Monoazo dye



Patented Aug. 23, 1932 EEINRIGHI'QHLENDOREDF vnnss,.m- 11v ANHALT, GERMANY, ASSIGNOR To, GENERAL autumn wonnsnm, or. NEW YORK, n. Y., A CORPORATION or DELAWARE ivro uonzo DYE No Drawing. Application filed. April '1, 1931, Serial No. 527,051," and in Germany April 11, 1930.

My present invention relates to a new process of manufacturing azo dyesland to the new dyes obtainable by this process.

According to my invention new monoazo dyes of very goodproperties are obtainable by transforming a 1.Q-naphthophenazine derivative substituted in naphthalene nucleus by the amino group and corresponding tothe general formula (in which the naphthalene and/or 'thejben- I With a compound-of any kind capable of I, 1 1

being coupled.

There can be used as coupling components inter alia hydrox'y or amino compounds of the naphthalene series, hydroxy compounds of the benzenefseries, pyrazolone derivatives or also aliphatic compounds capable of coupling, such as, ior instance, B-diketones such as acetyl acetone, and derivatives of acetoacetic acid ester. y Y

According'to the choice of the components, there canbe produced dyes dyeing a'great variety of tints anduseful for the most different fields of application, for instance,

6 W001 dyes, dyes for lake-making, pigments,

fat-soluble dyes etc.

The dyes are valuable owing to their'good fastness properties.

The- Wool 'dyes, for instance, are distin- "very 1 "sum of the jdiazo compound isrun, Wh le stirguishedby a good fastness to f lllllllg, ll( ),ll--

pressing and potting, and by an extra high zene series as coupling components.

iastness to rubbing of the dyelngs 1s remark -vthe 8-position of the i 23 B, into" the diazo compound which 'thejdiazotization is complete, isiprecipitated fastnessto light. Monoazo dyes of good fastness to light are already obtained with hydroxy compounds of the naphthalene orben- The able.

.The dyeswhich can be used as pigments .etc. (in the presence of sulfo-groups, for instance, also in the form of, their barium and calcium salts or the like) have a remarkable clarity of tint, good covering power and taste ness tolight. i l By a suitable selection of the components, the dyes can also be produced on a. suitable substratum, for instance, on the vegetable fiber.

The follovving examples illustrate theiinvention Without limiting it, the parts belng by W g tw H 4 E wample 1 ,3 4 .7 parts of sodiurnS-amino- 1.2-naphthophenazine-5 sulfonate of, the formula obtainable for instance, by condensing 8 a-cetylamino -1 .2 naphthoquinone 5 sulf onic acid (Which initself may be produced by reducing the nitroso' compound of S-acetylamino-1-hydroxynaphth'alene-5-sulonic acid and by oxidizing the amino compound formed) withLQ-diaminobenZene and by splitting off nitrite and 2a parts of hydrochloric acid of after in the form of feebly yellow} needlesbeing difiicultl'y soluble in ater; The suspenring, into an ice-cold solution of 25 parts of,

I e sodium 2- hydroxynaphthalene 6 sulfonate,

' Similar dyes are obtainable by substituting '2 hydroxynaphthalene-7-sulfonic acid or 1- L Ex to which a solution of 18 parts of sodium car- 7 bonate in 250 parts of water has been added. a After stirring for several hours, the dye is.

i V salted out. It forms in a dry state a red powder which dissolves in water to a yellowish-red solution and in concentrated sulfurlc acid to a ruby-colored solution. It dyes wool a tint of a good fastness to fulling and an unusually high; fastness to light.

The new dye as free acid probably corresponds to the formula:

hydroxynaphthalenel-sulfonic acid for the 2-hydroxynaphthalene-6sulfonie acid.- The dye prepared from 2-hydroxynaphthalene-7- sulfonic-acid dissolves in concentrated sulfuric acid to a red solution, that from V1-hydroxynaphthalener l-sulfonic acid to a dichroic greenish-red solution.

Ewa/mple 2-.'The diazo compound, wprei-pared according'to' Example 1 and correfsponding to 6.9parts of sodium nitrite, is filtered by suction, covered with a small quantity of water, then suspended in 400 parts of waterand introduced into an ice-cold solution, rendered feebly alkaline by means of sodium carbonate, prepared from 29 parts V of 1-acetylamino 8 hydro'xynaphthalene 4- sulfonic acid in 500 parts of water. After addition of a further quantity of 7 parts of sodium carbonate," the whole is stirred for several hours and the dye is then salted out. 7 It dissolves inconcentrated-sulfuric acid to a green solution- It dyes wool a Bordeaux tint fast to light and fulling.

Asfreeacid it probably corresponds to the formula V on lyn-ooom OaHI,

1 m a ioqaaiay bf thediazo (m pound 'obtained'accor'ding to Examplel and I correspondingto 6.9 parts of sodium nitrite, ;'is coupled with- 25. parts ofleaminonaphthalerie--sulfonicacid while adding an excess of sodium carbonate. 7 The dye dyes the anilow-red solution.

-pure yellow tints fast to light. V

isiae mal fiber brick-red tints. It dissolves in con centrated sulfuric acid to a greensolution.

As free acid it probably corresponds to the formula i V V EmampZe- -'4.-The same quantity of I the diazo compound is coupled with an alkaline solution of 11 parts of resorcine. The dye dyes' wool a clear yellowish-brown. It dis solves in concentrated sulfuric acid toa yel- -As free acid it probably corresponds to the formula v Example 5.The diazo compound obtained I according to Example 1,i s coupled with a solution of thesodium salt of sulfo-lphenyl-3-methyl-5-pyrazolone containing an] excess of sodium carbonate or sodium acetate. The dye is lsolated 1n the usual manner.

yellow solution and dyes the animal the formula;

' As free acid'it probably' corresponds to 7 03H V EmampZe quantity of the diazo compound, corresponding to 6.9 parts of sodium .7 nitrite, from 8-amino 1 .Q-naphthophenazihe- 5-sulfonic acid is suspended in water and the suspension is introduced, while well stirring, into 15 parts of 2 hydr'oxynaphthalene, Y

dissolved in the quantity of dilute sodium hydroxide solution required for dissolving it,

It dissolves in concentratedsulfuric acid to a fiber pleted addition of sodium chloride solution; the dye is then filtered and dried-or :made into a paste. 1n d-rycon-dition the dye dissolves in concentrated sulfuric acid to a dichroicred-blue solution and in water to a yellow-red solution. I-tdye's wool a clear brick-red tint.-

As free acid it probably corresponds to theformulaf I p The dye yields insolublebariuin salts and calcium salts which can be used as red pigments for oil colors or for printing wallpaper. The coatings and "prints thus obtained have a very good covering power and fastnes s to light.

Emample 7.,A;susp.ension of 18 parts of aceto-acetic acid anilideis mixed, while well stirring, with a quantity, corresponding to 6.9

parts of sodium nitrite, of the idiazo compound from 8 amino-1.2-naphthophenazine- 5-sulfonic acid and so muchjof sodium carbonate isadded theretothat thereis' an alkaline reaction when .the' coupli-ng i's complete.

The solate'd d e forms when dr a TQEIHSll- I u b yellow powder which dissolves 1n concenltrated sulfuric acid to a reddish-yellowfsoluotion and in water to azgreenishyellow solu- .tion.

7. As free acid it which is' approprl 7 probably "corresponds to the formula V 2-toluidideinstead of the anilide. Other de-.

rivatives of the aceto-acatic acid can be used" in an analogous manner.

E mample 8.Theaceto-actic' acid deriva-" tive in example 7 is replaced byl-phenyl-3- methyl-5-pyrazolone and a 'dye is obtained 'tedl'forxthe same'xpurposes;

the aceto-acetic acid- It yields reddish-ye'llow coatings.- The dry dye dissolves in concentrated sulfuric acid to a yellow solution.

As free acid it probably corresponds to the formula p i N H v N =N' J-oo11@ I EwampZe-9. A solution of partsof the sodium salt of .8-amino-l.2-naphthophena- Zine-5.5-disu1fonic acid (65 I (obtainable by condensing 8-acetyl amino-1.2-naphtho- 1 quin'one-dsulfonic acid with 1.2'd i amino benzene-5-sulfonic acid and splitting off the acetylfradicle) in 400 parts of water, is dia'zotized in the usual manner with 7 parts of nitrite" and 24 parts of hydrochloric acid of-- 1 23 B. The feebly yellowish diazo solution is run into an ice-cold solution of 15 parts of Q-hydroxynaphthalene and the correspondin g quantity of of water, are added thereto. The dye is isolated in the usual manner. It dissolves'in water to a yellow-red solution and inconcentrated sulfuric acid to a solution which is violet by transmitted light and blue by reflected light.

sodium hydroxide in 600 parts wool are similar to those of Example 1.

As free acid it probably corresponds to the formula v y l SO33 The analogous dye from -l-hydroxynaphthalene dyes the animal fiber'BordeauX tints;

it dissolves in concentrated sulfuric acid to a marine blue solution.

and20 parts of sodium carbonate i The tints and other properties of, the dyeings on Ewample 10.-Thediazo compound of EX:

ample 9 is caused to act upon the correspond ing quantity of a suspension of l-phenyl-3 1nethyl-5-pyrazolone anda quantity of sodi- Yum carbonate more than'required for ncutrallzingthe ac1d 1s addedthereto- The dye ajcidto' a reddish-yellow solution and dyes wool a reddish-yellow tintof goodf'astness properties; r V

dissolves" in waterand concentrated sulfuric i is ' ample 9 is coupled with thecorresponding 1 As free acid it 1 Asfr'ee aciditprobably corresponds to the fonic acid (prepared from l acetamino-8- hydroxynap'hthalene2;4-disulfonic acid by introducing the nitroso-group, reducing and oxidizing) j .with ";'l-.2 di;aminobenzene I and splitting off the a-cetyl group itdissolve'sin Water to ayellow solution and in concen- 1 diazo compound of Example 9 is run into an i .i'ce-coldsolutionof 18 parts of aceto-acetic acid anilide, dissolvedin the equivalent quantity of'dilute sodium hydroxide solution, while adding a quantity of sodium carbonate being more-than suflicient for coupling." The dye is workedup in the usual manner. It. dissolves in concentrated'sulfuric acid toan orange-red solut1on,-1n water to a greenish- .yellow solution anddyes wool a clear pure yellow of good fastness properties.

probably corresponds to the formula:

SOaH

v V so'an 7 Example 12.The diazo compound of Exquantity of QA-dihydroxy-quinoline. The

' dye 'dissolvesiin water and in concentrated formula sulfuric acid to a yellow-red solution. It dyes the animal fiber yellow-red tints of good fastness properties.

As free acid it probably corresponds to the Example 13.4mm is used instead of the 8-amino' 1.Q-naphthophenazine-disulfonic 1 acid of Example 9 the 8-'amino-1 .2-naphtho-v phenazine-5.7-disulfonic acid; the latter can. r

v beobtained, for instance, by condensing 6 8-acetylamino- 1.2-naphthoquinone-SJ-disuh 5' trated sulfuric acidto a greenish-yellowsolw tion.- The dye produced by"coupling' vvithQ-hydroxynaphthalene' dyes wool a brownishyellow tint of good fastness properties- It dissolves in'sulfonic acid toa Bordeaux red solution.

, As free acid probablylcorresponds to 8b the formula loan The dye from 1-phenyl-3 iirethyl-5 pyrazolone dyes the animal fiber clear reddish-yellow tints. It dissolves inconcentrated sul- 'furic acid to a yellow solution.

Example" 14. The sodium salt of S-amino-5-chloroel.2 -naphthophenazine-5-su1fonieacid'is prepared, for instance,;by condensing 8 acetylamino-l.2-naphtho'quinone 5rsulfonic acid with 1.2-diamino-4-chlorobenzene and subsequentlysplitting ofl the acetyl group; it is brick-red and dissolves in water to a yellowish-red solution and in concen- I trated sulfuric acidto a greenish-yellow solution. 38 parts of this compound are diazotiz'ed in the usual manner with hydrochloric acid and 6.9 parts of nitrite and the difficultly 7 soluble diazocompound suspended in water,

naphthalene 6 sulfonate,in the presence of an excess of sodium carbonate. After stirring for several hoursthedye mav besalted out. It dissolves in concentrated sulfuric is coupled with 25 parts of sodium Q-hydroxyacid to a ruby-colored solution and in water to a yellowish-red solution. It dyes the animal fiber red tints, analogously to the dye obtained in Example '1 i As free acid it proloablycorresponds to :1

the formula r Eeamfle 15.. -Th e" sodium salt of 8 -aminoe 1m .-1.2 naphthophehazine 5 sulfonic I SOzlElI SOaH Example 16'.50 parts of 8-amino-1.2-.

naphthophenazine base are well stirred with 300 parts of water and 7 5 parts of hydrochloric acid of 23 B. ,After the colorless hydrochloride has been formed, 14 parts of sodium nitrite in 900 parts of water are gradually added at about 10 C. whereby a yellow solution of the diazo compound is formed. It is run, while stirring, into a solution of 7 0 parts of the neutral sodium salt of the Q-hydroxynaphthalene-3.6-disul- 'fonic acidcontaining a quantity of sodium carbonate which is more than suflicient for binding the acid. The dye is salted out after several hours. It dissolves in concentrated sulfuric acid to acherry-red solution and dyes wool-a. Bordeaux of good fastness to fulling and light. 3 g As free acid it probably corresponds to the formula:

SOaH SOsH By coupling the same diazo compound with l-hydroxynaphthalene-3.8-disulfonic acid, a dye is obtained which dissolves .in concentrated sulfuric acid to a dichroicredgreen solution and dyes wool a bluish-red tint fast to fulling' and light.

' Example I/.A solutionfof the diazo compound,corresponding to 6.9 parts of sodium nitrate and, if required, filtered, from S-amiwith Q-hydrOXynaphthaIene-G fastnessto light.

no-l2-naphthophenazine is run, while stir: ring, into a solution of. 19.5 parts-ofacetoace; tic. acidQ-toluidide in the equivalent quantity of dilute sodium hydroxide solution and the free acid is bound by an excess of sodium car bonate or sodium ecetatc. After the'coupling is complete" the dye is"- filtered, washed and made into a paste or dried. T he. coupling can also be carried out in thep'resence of disper sion agents, suchfas Turkey red oil or the like.

The dry dye forms'a'reddish yellow powder which dissolves inconcentratedsulfuric acid to a yellowish-redsolution. It probably corresponds to the. formulae:

i. The dye is practically insoluble alcohol and linseed oil. It can be'used'witho'r without additions as pigmentl of' good "covering' power-and fastnessfto light 'for goil'colors or for printing wallpaper. Any 'ofth'e usual substrata adaptedfor the productionof'lake's can. already be'added when preparing the dye. v

Ewa/mplc l $.----The diazo compound used in Example 16 is caused to act upon the corresponding quantity of a solution of 'Q-hydrOX- ynap'hthalene containing an excess of alkali. The dye formedis, in dry condition, ared powder soluble in concentrated sulfuric acid to a solution which is'redby transmitted light and green by reflected light. It dissolves in alcohol and indifierent organic solvents to deep yellowish-red solutions; In a mixture of stearin and ceresin fit-dissolves while hot to a solution of thes'arne coloration. Dyed masses of'this kind have a remarkable Probably it corresponds to "the formula Emample 19.Cot ton,.:is impregnated in known manner with an alkaline solution of 2- 9 hydroxynaphthalene 3-carboxylic acid-phe nylamide and is-"then treated with a diazo solution of 8-ami-noTLQ-naphthOphenaZine,

wherein the free mineral acid has been neu tralized by means of sodium acetate. A redspends tothe formula:- I r dishrawn tint of af 'ood fastness a; light and to kier-boiling is-obtainedj;

:'The dye thus formed on the fiber-poise,

By using "the preceding example for paddingan alkaline solution ofdiacetoacetic acid-ortho-tolidinide, a gold-colored tint of similar fastness' propertiesis obtained; by

using'an alkaline solution of one of the hydroxy-azine compounds,-for instance, of the compound produced by alkaline fusion of a-hydroxy-8-sulfonaphtho-3 or 5-aminophenazine, a neutral brown of good fastness properties is obtained.

It is obvious that my invention is not limited to the foregoing examples or to the details given the rein.- Though Ihave en.um-.

V erated in. these examples a, greatnumber of compounds of different groups capable to be coupled with teh diazo compounds in,ques tion, itmay bestated'that other azofcomponents,isuch as, for instance, hydroxy or arm ino or hydroxyaminocompounds of the benzene or naphthalene series'may beused which aresubstituted in the nuclei by, for instance,

halogen, alkyl, nitro, carboxy, oxyalkyl or 7 similar radicles. On the other hand, 8-ami-' no-1.2-naphthophenazine compounds other than those'mentioned in the examples, may be used as diazo component. In this case,

likewise, the nuclei may be substituted by the radicles enumerated above with respect to the azo components. Finally, Inna-y use such an amino compound in which the sulfonic acid group orgroups have a position. -e1ther in thenaphthalene or in the benzene monoazo dyes corresponding probably to the general formula general formula:

by the claims following herevwherein R means anazocomponent and X stands for hydrogen "or a 5 univalent substituent of the group 'consistin g o f sulfo, c,arboxy," l halogen, nitro, alkyh'andoxy alkyl';

I 2."A s new "articles of manufacture the monoazo dyes correspondingprobably to wherein R means an azo component, w stands.

for hydrogen or sulfo and 04 for hydrogen or a substituent of-the group consisting of sulfo, halogen, nitro, alkyl" and oxyalkyl.

3. As new articles off manufacture the monoazo dyes corresponding probably to the general formula:

wherein R represents an azo component of the naphthalene seriesmstandsfor hydrogen or sulfo and w for hydrogen'or a substituent of the group consisting of sulfo, halogen,

' nitro, alkyl, and oxyalkyl.

'4. As new articles of manufacture the monoazo dyes corresponding probably to the general formula: i

wherein R represents hydrozrynaphthalene E-compound, m stands for hydrogen or sulfo and w for hydrogen or a substituent of the group consisting of sulfo, halogen, nitro,

alkyl and oxyalkyl. a V 5 new articles-of manufacture the monoazo dyes corresponding probably to the general formula: v.

I wherein R represents a hydroxynaphthalene sulfonic acichm stands for hydrogen or sulfo and w for hydrogen or a substituent of the I group consisting of sulfo, halogen, nitro,

alkyl, and oxyalkyl.

6. As new articles of manufacture the monoazo dyes corresponding probably to the general formula:

wherein R represents a B-hydroxynaphthalene sulfonic acid, w stands for hydrogen or snlfo and w for hydrogen or a substituent of the group consisting of sulfo, halogen, nitro, alkyl, and oxyalkyl.

7 As a new article of manufacture the monoazo dye corresponding as free acid to the formula (l forming in the d'ry pulverized state a red powder insoluble in water, soluble in concen trated sulfuric acid to a solution which is red by transmitting light and 'green byre:

I flected'light, being likewise sol'ublein alcohol to a deep'yelloWish-rd s lution. 9; A's-new articles of manufacturefthe monoazo dyes corresponding as free acids probably tothe general formula": v

I S0311 1 N .1 (51:61 I v R i S0311 wherein R represents the phenyl i or tolyl radicle, being in the dry pulverized state a dark powder, soluble in concentratedsulfuric acid to. an orange-red solution in water to a greenish-yellow solution, and dyeing wool clear yellow tints of good fastness.

10. The'process which comprises diaz otize ing an 8-amino-1.2-naphthophenazine com-' pound and reacting the diazo compound obtained upon a compound capable of being coupled with a diazo compound with the formation of an azo dye.

11. The process which comprises diazotizing an 8-amino-1.Q-naphth phena ine compound and reacting the diazo compound obtained upon a hydroxy compound of the genformation of an azo dye.

SOsH forming in the dry, pulverized state a. red powder, soluble in water to yellowish-red solution and in concentrated sulfuric acid to a ruby-colored solution and dyeing wool red shades fast to fulling and having an unusually high fastness to light.

8. As a new article of manufacture the manoazo dye corresponding to the formula:

13. The process which comprises diazo tizing an S-amino-l.Q-naphthophenazine sulfonic acid and reacting the diazo compound obtained upon a compound capable of being coupled with a diazo compound with the for mation of an azo dye.

14. The process which comprises diazotizing an 8-amino-1.Q-naphthophenazine sulfonic acid and reacting the diazo compound obtained upon a hydroxy compound of the general'formula HO-R, wherein R means a radicle of the group consisting of phenyl and naphthyl.

15. The process which comprises diazotizing an 8-amino-1.Q-naphthophenazine sulfonic acid and reacting the diazo compound obtainedupon ahydroxynaphthalene.

16. The process which comprises dia zotizing an 8amino-1.2-naphthophenazine sulfonic acid and reacting the diazo compound obtained upontizing -fonicacid.-

c g 17. The process which comprises diazotiz ing an 8-amino-1.2 naphthophenazine sulfonioa'cid and reacting'the diazo Compound Obtained upon a' keto compound capable of 'being coupled with}, diazo' compound IthQformattion of anazo dye. 18. The processcwhich comp'nsesdiazotizing 8-aminoe1.2-naphthophenazine-5-sulfonic acid and coupling'the diazolcompound'olotained with 2-hydroxynaphthalene-5-su1fon-' ic acid in an alkaline solution.

19. The process which comprises diazo- 8-amino-1.Z naphth PhenaZine-5.5- H disulfonic acid" and coupling" the diazo compound obtained with aceto-acetylphenylamide in an alkaline solution.

20. The process which comprises diazotiz- 7 ing 8 amino- 1.2 naphthophenazine and couplingthe diazo compound obtained with fihydroxynaphthalene in an alkaline solu- 1 tion. v

In testimony whereof, I aflix my signature.

' J EINRIC OHLENDORF;

2i hydroxynaphthalene sul with 

